CA1095904A - Process for the manufacture of crystalline fructose - Google Patents
Process for the manufacture of crystalline fructoseInfo
- Publication number
- CA1095904A CA1095904A CA348,491A CA348491A CA1095904A CA 1095904 A CA1095904 A CA 1095904A CA 348491 A CA348491 A CA 348491A CA 1095904 A CA1095904 A CA 1095904A
- Authority
- CA
- Canada
- Prior art keywords
- fructose
- solution
- glucose
- weight
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K11/00—Fructose
Abstract
ABSTRACT OF THE DISCLOSURE
A process for the manufacture of free-flowing crys-talline fructose, which process comprises seeding an 88% to 96% by weight fructose syrup with 2% to 15% by weight of fructose seed crystals at 120°F to 160°F, the seed crystals having a size not greater than 250 microns, and permitting crystallization to occur at about 50°F to 90°F and at a rela-tive humidity of less than 70%.
A process for the manufacture of free-flowing crys-talline fructose, which process comprises seeding an 88% to 96% by weight fructose syrup with 2% to 15% by weight of fructose seed crystals at 120°F to 160°F, the seed crystals having a size not greater than 250 microns, and permitting crystallization to occur at about 50°F to 90°F and at a rela-tive humidity of less than 70%.
Description
~L~g~i9~
Crystalline fructose is commercially manufactured by a very involved and time-consuming crystallization process which requires relatively sophisticated processing machinery and apparatus and careful control of process conditions, to en~ure the production of a satisfactory crys-talline-fructose product.
As is well known, anhydrous fructose crystals may be obtained by crystallization of the fructose from both aqueous solutions and aqueous alcohol solutions, such as aqueous methanol and aqueous ethanol solutions o~ ~ructose. The employment o~ sol-vents in ~ructose solutions is undesirable, both from theeconomic point of view and since the resulting crystals pre-cipitated from the solution and the liquid containin~ the sol-vent must have the solvent completely removed pxior to consump-tion or use of the crystalline ~ructose, while economic opera-tions also dictate the removal of the solvent from the mother liquid for use in the process.
A number of processes have been proposed in connec-tion with the production of crystalline fructose from aqueous solutions. Mowever, none of said processes has been satis-factory wholly, since they involve a number and a variety ofprocess steps and careful control of various process-operating conditions and typically result in only very low yields of crystalline fructose.
For example, as disclosed in U~ S. Patent 3,513,023, crystalline fructose is produced through the employment of a fructose solution having at least 95% by weight fructose con-centration, which is further concentrated in a vacuum to a water content of from about 2% to 5% and then cooled to a temperature of from about 60F to 80F. A large quantity of the crystals are then added to the concentrated, cooled solution, and the mixture then must be stirred at a low temperature until it becomes a soft mass. This mass then is made solid and is dried ~9s~
at a temperature below about 150F. The p~opose~ process is not satisfactory where it is essential to the p~ocess that the fructose concentration be not less than 95%, that kneading of the soft mass occur and further that only pure crystalline fructose seed crystals be employed. The proposed me-thod thus has disadvantages both in terms of material handlin~ and high-energy costs, as well as being limited to the employment of pure fructose syrups.
Another ~ructose process is described in U. s. Patent 3,883,365, which is directed ~o ~he process of the production of crystalline fructose ~rom an aqueous solution, and whic~
process involves providing a saturated fructose solution, ad-justing the pH of the saturated solution within a pH of 4.5 to 5.5, and then seeding the solution with fructose crystals, and, thereafter, lowering the temperature of the solution and optimally evaporating the solution to cause the formation of crystalline fructose. The resulting crystalline fructose is then separated by centrifuge methods. This process requires a very careful controlled-temperature cooling of the over 90/O
fructose solutlon to generate crystals and to increase the crystal size. Seed crystals must be pure fructose crystals of low crystalline size, and the yield produced is typically less than about 50%. Periodically, the process must be stopped and the solution, from which crystallization is being carried out, diluted with additional water, to avoid supersaturation levels of the solution. The essence of the invention involves a criticality of the pH and -the need to adjust the pH to the range of 4.5 to 5.5.
A further method for obtaining anhydrous fructose crystals is set forth in U. S. Patent 3,928,062, which is some-what similar to the process described in U. S. Patent 3,883,365, wherein crystalline fructose is produced from a supersaturated ~959~
fructose solution, seeding anhydrous crystals into the solution and then concentrating and/or coating the solution while main-taining the sugar concentration and the temperature in the liquid phase within a carefully defined range, and then recov-ering the anhydrous crystals from the mass. Once again, the yield is typically under 60~/o, while the disadvantages of the process also require precise control o process variables, such as the rate of cooling and the rate of evaporating, and the syrup concentration is limited to less than 90% by weight, in order to avoid supersaturated solutions.
A further process is also described in U. S. Patent 3,929,503, wherein a method is provided to obtain free~flowing anhydrous particles of glucose, fructose or mixtures thereof in such rorms as powder, pellets, granules and the like, with-out subjecting the solution to a crystallizatior. step. The process involves kneading of crystals or powder of anhydrous glucose, fructose or mixtures thereof, that is, a mother powder, with a syrup containing 40% to 90% of the same type of sugar as the mother powder, so that the resulting mixture forms wet particles having a moisture content of less than about 7%.
The disadvantage of this particular process is that, even in the case of the most favorable concentration of 95%, it is recognized that it is very difficult to distribute uniformly the power, due to the practical difficulties of admixture, such as, for example, the very high viscosity. Once again the yield is only about 54%, as the remaining material must be recycled as the mother powder, and both energy costs and material-handling costs are much higher, because of the poor yield.
Therefore, it would be most desirable to provide a process for the production of crystalline fructose, which pro-cess avoids the many disadvantages of the prior-art processes, and which process would present a simple and economical process ~, 9~4 avoiding the large capital and equipment costs and the careful process-control conditions associated with the prior-art pro-cesses.
Our invention relates to a process for the manufac-ture of free-flowing, anhydrous, crystallina fructose and mixtures of crystalline fructose and glucose. In particular, our invention concerns an improved, economical process for the preparation of a free-flowing, anhydrous, crystalline fructose from concentrated ~ructose, and high-~ructose corn-syrup solutions.
Our process concerns the manufacture of free-flowing, anhydrous, crystalline fructose or high-fructose corn-syrup solids, which process comprises seeding ~8% to 96% by weight of a syrup-containing aqueous solution with a seed of the same or of a major sugar, in the case of an impure mixture of the syrup solution, of a size not greater than about 250 microns and typically about 150 microns or less and in an amount of from about 2% or more; for example, 2% to 15% by weight, based on the total solids present in the syrup solu-tion, and allowing crystallization to take place in a periodof time or from about 2 to 72 hours, depending upon the type and size of the seed crystals employed, percent relative humidity and temperature and the moi.sture content of the high-fructose, corn-syrup solution used, and, thereafter, recovering the resulting crystalline material so produced and drying and size-reducing, such as by grinding, said crystalline material, to produce an anhydrous, free-flowing fructose or mixtures of fructose and glucose.
In accordance with a broad aspect of the invention, there is provided a process for the manufacture of an anhydrous, free-flowing crystalline, fructose-containing material, which process comprises:
~ l - 4 -' '. ' .
a) providing an aqueous fructose-containing composi-tion having a weight of from about 88% to 96% by weight of fructose or a mixture of fructose and glucose, and which solu-tion is essentially free from discoloration, b) seeding said fructose-containing solution with from about 2% to 15%, based on the total weight of the solu-tion, with seed crystals of the same general composition as the composition of the solution, ana having a particle size of not greater than about 250 microns and at a temperature of from about 120F to 160~F, c) permitting such seeded syrup solution to stand at about 50F to 90F and at a relative humidity below 70%, to provide for substantial crystallization of the fructose and/or glucose in the solution, and, thereafter, d) recovering the crystallized fructose from the crystallization solution and drying the fructose so recovered, to provide for a free-flowing anhydrous, crystalline fructose or mixture of fructose and glucose.
The process of our invention provides a simple and economical method of providing free-flowing, anhydrous particles of fructose or mixtures of glucose and fructose, through a simple seeding and crystallization step, and avoids the diffi.-~ I - 4a -S9(34 culties associated with prior art process.
The aqueous fructose, and high-fructose corn-syrup composition employed in the process should comprise from 88%
to 96% by weight of the fructose or fructose/glucose mixture, an~ typically from about 90% to 95% by weight, while the most preferred concentration ranges from about 92% to 94% by weight.
The aqueous corn-syrup composition should be brought to the desired solids content, and, in the event that any heating or cooking is required to so adjust the solids content, such heat-ing or cooking should be carried out preferably under vacuumand at a temperature of not more than 200F, in order to avoid any discoloration in the resulting syrup solution, which dis-coloration retards the crystallization. The syrup solution may comprise fructose, a mixture of fructose and glucose, for example, a high-fructose corn-syrup solution.
It is essential, in the practice of the invention and process that, during crystallization, the relative humidity should be maintained below 70%, for example, preferably below 50% and most preferably between 35% to 45%, and the surrounding temperature should be maintained either between 50F to 90F
or sequentially decreased to this range or lower. The seed size of the crystals should not be greater than 250 microns, and typically less than 200 microns, such as, for example, from about 50 to 150 microns. It has been discovered that a larger size of the seed crystals does not lead to crystalliza-tion of the material from the aqueous syrup solution in any reasonable time period, and, therefore, affects the commercial viability of the process~ In addition, the amount of the seed crystals employed is a critical effect on the ease of drying of the final crystalline material produced in the process. It has been discovered further that the amount of seed crystalline and the moisture content of the syrup solution becomes signifi-cant in terms of crystallization time, when the seed crystals do not have the same contents or represent the same type of crystals as that employed in the syrup solution. It has been found that the amount of seed crystals employed should be greater than 2% by weight, based on the total solids present in the syrup solution, and more particularly should range from 5% to 15% by weight, which is the preferred amount em-plo~ea .
The seed crystals employed in the process may bederived from any source, but typically should represent pure fructose crystals, a mixture of glucose and fructose crystals, or should represent a part of the ~inished crystalline product obtained in the process and recycled in a subsequent crystalli-zation process. In any event, it is important to employ the seed crystals in the same general type, character and nature of that of the composition of the sugar in the aqueous syrup composition, since variations in the nature of the seed crys-tals from that of the syrup composition affect the crystalliza-tion time.
Typically the seed crystals should be added to the syrup composition, when the syrup composition is at a tempera-ture ranging from about 120F to 160~F, and more particularly about 130F to 140F. The syrup composition, after seeding, may be deposited in a mold or other suitable container and then allowed to sit at 50F to 80F and a relative humidity of 35%
to 45% for a crystallization time from about 6 to 72 hours.
Pure fructose syrups may take only a short period of time, for example, as low as 3 to 4 hours, while corn-syrup compositions, that is, containing a mixture of glucose and fructose, typically take a longer period of tlme, such as, for example, 36 to 72 hours. At the end of such crystallization time, the crystalline material is recovered and dried, with the method of drying de-pending upon the moisture content desired in the final product, ~Q~S~4 and then ground to produce the free-flowing, anhydrous, cr~s-talline fructose and glucose of the invention. If desired and preferably, a small percentage of the recovered material then may be recycled and used as a seed crystal with the same type of syrup composition.
In regards to the concentration range of the syrup composition, the syrup concentration is critical, since it has been discovered that, if the range is generally below about 88% by weight, the solution remains pasty, even after the addi-tion of seed crystals, and any crystallization produced is in apaste-type form which is hard and impossible to bring into a dry, free-flowiny, anhydrous, powder form. I-f the syrup com-position exceeds g~nerally about 96% by weight, the s~rup com-position remains as a rather glassy-type syrup mixture. During the crystallization time, the seeded syrup mixture is allowed to sit generally at temperatures of ~rom about 60F to 85 F
such as, for example, 70F to 80F and a relative humidity of 35% to 45%, until substantial crystallization takes place, with the physical condition of the final crystalline product depending in part upon the moisture content of the starting syrup solution.
It has been found that the crystalline product pro-duced by the process is formed in large pellets in the crys-tallization process' for example, about 3 grams in weight, and the crystallization pellets so formed are quite heat-sensi-tive. The crystallization pellets have been found not to lose moisture during drying a~ter a certain moisture content is reached; for example, 3% to 5%. For example, hemispherical pellets, with a base diameter of about 0.75 inches, do not lose moisture beyond about 3%. Attempts to dry such pellets to a lower moisture content, by subjecting the pellets to higher drying temperatures and vacuum, have been unsuccessful, ~ 9 5~ ~ ~
as the surface tends to dry, but the inside material of the pellets only soft~ns.
It has been ~ound that the heat-sensitive, water-soluble crystallization pellets of the process may be dried to a desired moisture content by cooling the pellets to a temperature below about 34F and then granulating the pellets, such as by grinding, to less than 18 mesh. ~h~r~after, the ground pellets may be dried in a low relative humidity, for example, less than 50%, such as 35% to 45%, at oven tempera-tures; for example, 110F to 160~F, to provide free powdered material with a low moisture content, for example, 0.5% to 2%.
Thus the high heat sensitivity of the crystallization pellets makes the product difficult to grind, since the product tends to melt due to heat buildup in the grinding mill. However, the pellets, when cooled to 34F or below, may be ground, and, thereafter, may be dried in conventional ovens to a low mois-ture content.
For the purpose of illustration only, our process will be described in connection with certain preferred operat-ing embodiments; however, it is recognized that various changesand modifications in the process, as described and illustrated, may be made by those persons skilled in the art, all within the spirit and scope of our invention.
Example 1 The term "high-fructose corn syrup" used in this example is used for the following commercially available pro-duct:
Dry Basis Composition Ash (Sulfated) .03%
Carbohydrate components:
Fructose 90%
Dextrose 7%
Other saccharides 3%
Typical analysis:
Solids 80%
Moisture 20%
,, ~ .
~ , .
~S9~4 The syrup was cooked to a moisture content of 92 ~
0.5% and seeded with 5% seed of a size of 177 to 250 microns.
The product was placed in molds and allowed to sit at 78F
and a relative humidity of 30%. The crystalliæation commenced in 24 hours. The resultant product was dried in a vacuum oven maintained at 29" of Hg. The temperature was gradually in-creased from 70F to 200F in 16 hours. The product was worked up to the required par~icle size, Free-flowing, nontacky, crystalline material was obtained.
Some cooked syrup was seeded with the product obtain-ed above the crystallization time reduced to 8 hours.
Example-2 Pure fructose was dissolved in water to obtain a syrup o~ 95% solids content. This was seeded with 5% crystal-line fructose of a size of 74 to 177 microns, deposited in molds and was allowed to sit for 72 hours at 80F and a rela-tive humidity of 45%, and then worked up and dried in the oven by gradually increasing the temperature ~rom 70F to 200F in 4 hours. The product was free-flowing and nontacky.
Exam~le 3 Pure fructose was dissolved in water to obtain a syrup o~ 93% solids content. It was brought to a temperature of 140F and seeded with 10% crystalline fructose of a size of 74 to 174 microns. The resultant material was deposited in molds and allowed to crystallize at 85F and a relative humid ity of 45%. After 12 hours, it was dried and ground. The product was free-flowing, nontacky and crystalline.
Example 4 A 2-pound sample of the crystallization-pellet mat-erial of the process was cooled and ground in a domestic blend-er. The resulting powder was then screened through an 18-mesh screen. The undersized product was dried in a temperature-g _ , '::
`': ' ., ,~ , 5gO~
controlled oven in the presence of circulating air as follows,to provide a low, moisture-free, flowing product:
TIME TEMPERATURE MOISTURE CONTENT
8 110F 2%
4 150F 1%
Attempts to dry the same pellet material, by con-ventional oven-drying of the pellets to low moisture content, were unsuccessful.
As can be seen by the aforesaid data and examples, the syrup concentration and the nature of the seed crystals and crystallization conditions and more specifically relative humidity are essential conditions, in order to produce and provide for the advantages of our process.
r .: ~
Crystalline fructose is commercially manufactured by a very involved and time-consuming crystallization process which requires relatively sophisticated processing machinery and apparatus and careful control of process conditions, to en~ure the production of a satisfactory crys-talline-fructose product.
As is well known, anhydrous fructose crystals may be obtained by crystallization of the fructose from both aqueous solutions and aqueous alcohol solutions, such as aqueous methanol and aqueous ethanol solutions o~ ~ructose. The employment o~ sol-vents in ~ructose solutions is undesirable, both from theeconomic point of view and since the resulting crystals pre-cipitated from the solution and the liquid containin~ the sol-vent must have the solvent completely removed pxior to consump-tion or use of the crystalline ~ructose, while economic opera-tions also dictate the removal of the solvent from the mother liquid for use in the process.
A number of processes have been proposed in connec-tion with the production of crystalline fructose from aqueous solutions. Mowever, none of said processes has been satis-factory wholly, since they involve a number and a variety ofprocess steps and careful control of various process-operating conditions and typically result in only very low yields of crystalline fructose.
For example, as disclosed in U~ S. Patent 3,513,023, crystalline fructose is produced through the employment of a fructose solution having at least 95% by weight fructose con-centration, which is further concentrated in a vacuum to a water content of from about 2% to 5% and then cooled to a temperature of from about 60F to 80F. A large quantity of the crystals are then added to the concentrated, cooled solution, and the mixture then must be stirred at a low temperature until it becomes a soft mass. This mass then is made solid and is dried ~9s~
at a temperature below about 150F. The p~opose~ process is not satisfactory where it is essential to the p~ocess that the fructose concentration be not less than 95%, that kneading of the soft mass occur and further that only pure crystalline fructose seed crystals be employed. The proposed me-thod thus has disadvantages both in terms of material handlin~ and high-energy costs, as well as being limited to the employment of pure fructose syrups.
Another ~ructose process is described in U. s. Patent 3,883,365, which is directed ~o ~he process of the production of crystalline fructose ~rom an aqueous solution, and whic~
process involves providing a saturated fructose solution, ad-justing the pH of the saturated solution within a pH of 4.5 to 5.5, and then seeding the solution with fructose crystals, and, thereafter, lowering the temperature of the solution and optimally evaporating the solution to cause the formation of crystalline fructose. The resulting crystalline fructose is then separated by centrifuge methods. This process requires a very careful controlled-temperature cooling of the over 90/O
fructose solutlon to generate crystals and to increase the crystal size. Seed crystals must be pure fructose crystals of low crystalline size, and the yield produced is typically less than about 50%. Periodically, the process must be stopped and the solution, from which crystallization is being carried out, diluted with additional water, to avoid supersaturation levels of the solution. The essence of the invention involves a criticality of the pH and -the need to adjust the pH to the range of 4.5 to 5.5.
A further method for obtaining anhydrous fructose crystals is set forth in U. S. Patent 3,928,062, which is some-what similar to the process described in U. S. Patent 3,883,365, wherein crystalline fructose is produced from a supersaturated ~959~
fructose solution, seeding anhydrous crystals into the solution and then concentrating and/or coating the solution while main-taining the sugar concentration and the temperature in the liquid phase within a carefully defined range, and then recov-ering the anhydrous crystals from the mass. Once again, the yield is typically under 60~/o, while the disadvantages of the process also require precise control o process variables, such as the rate of cooling and the rate of evaporating, and the syrup concentration is limited to less than 90% by weight, in order to avoid supersaturated solutions.
A further process is also described in U. S. Patent 3,929,503, wherein a method is provided to obtain free~flowing anhydrous particles of glucose, fructose or mixtures thereof in such rorms as powder, pellets, granules and the like, with-out subjecting the solution to a crystallizatior. step. The process involves kneading of crystals or powder of anhydrous glucose, fructose or mixtures thereof, that is, a mother powder, with a syrup containing 40% to 90% of the same type of sugar as the mother powder, so that the resulting mixture forms wet particles having a moisture content of less than about 7%.
The disadvantage of this particular process is that, even in the case of the most favorable concentration of 95%, it is recognized that it is very difficult to distribute uniformly the power, due to the practical difficulties of admixture, such as, for example, the very high viscosity. Once again the yield is only about 54%, as the remaining material must be recycled as the mother powder, and both energy costs and material-handling costs are much higher, because of the poor yield.
Therefore, it would be most desirable to provide a process for the production of crystalline fructose, which pro-cess avoids the many disadvantages of the prior-art processes, and which process would present a simple and economical process ~, 9~4 avoiding the large capital and equipment costs and the careful process-control conditions associated with the prior-art pro-cesses.
Our invention relates to a process for the manufac-ture of free-flowing, anhydrous, crystallina fructose and mixtures of crystalline fructose and glucose. In particular, our invention concerns an improved, economical process for the preparation of a free-flowing, anhydrous, crystalline fructose from concentrated ~ructose, and high-~ructose corn-syrup solutions.
Our process concerns the manufacture of free-flowing, anhydrous, crystalline fructose or high-fructose corn-syrup solids, which process comprises seeding ~8% to 96% by weight of a syrup-containing aqueous solution with a seed of the same or of a major sugar, in the case of an impure mixture of the syrup solution, of a size not greater than about 250 microns and typically about 150 microns or less and in an amount of from about 2% or more; for example, 2% to 15% by weight, based on the total solids present in the syrup solu-tion, and allowing crystallization to take place in a periodof time or from about 2 to 72 hours, depending upon the type and size of the seed crystals employed, percent relative humidity and temperature and the moi.sture content of the high-fructose, corn-syrup solution used, and, thereafter, recovering the resulting crystalline material so produced and drying and size-reducing, such as by grinding, said crystalline material, to produce an anhydrous, free-flowing fructose or mixtures of fructose and glucose.
In accordance with a broad aspect of the invention, there is provided a process for the manufacture of an anhydrous, free-flowing crystalline, fructose-containing material, which process comprises:
~ l - 4 -' '. ' .
a) providing an aqueous fructose-containing composi-tion having a weight of from about 88% to 96% by weight of fructose or a mixture of fructose and glucose, and which solu-tion is essentially free from discoloration, b) seeding said fructose-containing solution with from about 2% to 15%, based on the total weight of the solu-tion, with seed crystals of the same general composition as the composition of the solution, ana having a particle size of not greater than about 250 microns and at a temperature of from about 120F to 160~F, c) permitting such seeded syrup solution to stand at about 50F to 90F and at a relative humidity below 70%, to provide for substantial crystallization of the fructose and/or glucose in the solution, and, thereafter, d) recovering the crystallized fructose from the crystallization solution and drying the fructose so recovered, to provide for a free-flowing anhydrous, crystalline fructose or mixture of fructose and glucose.
The process of our invention provides a simple and economical method of providing free-flowing, anhydrous particles of fructose or mixtures of glucose and fructose, through a simple seeding and crystallization step, and avoids the diffi.-~ I - 4a -S9(34 culties associated with prior art process.
The aqueous fructose, and high-fructose corn-syrup composition employed in the process should comprise from 88%
to 96% by weight of the fructose or fructose/glucose mixture, an~ typically from about 90% to 95% by weight, while the most preferred concentration ranges from about 92% to 94% by weight.
The aqueous corn-syrup composition should be brought to the desired solids content, and, in the event that any heating or cooking is required to so adjust the solids content, such heat-ing or cooking should be carried out preferably under vacuumand at a temperature of not more than 200F, in order to avoid any discoloration in the resulting syrup solution, which dis-coloration retards the crystallization. The syrup solution may comprise fructose, a mixture of fructose and glucose, for example, a high-fructose corn-syrup solution.
It is essential, in the practice of the invention and process that, during crystallization, the relative humidity should be maintained below 70%, for example, preferably below 50% and most preferably between 35% to 45%, and the surrounding temperature should be maintained either between 50F to 90F
or sequentially decreased to this range or lower. The seed size of the crystals should not be greater than 250 microns, and typically less than 200 microns, such as, for example, from about 50 to 150 microns. It has been discovered that a larger size of the seed crystals does not lead to crystalliza-tion of the material from the aqueous syrup solution in any reasonable time period, and, therefore, affects the commercial viability of the process~ In addition, the amount of the seed crystals employed is a critical effect on the ease of drying of the final crystalline material produced in the process. It has been discovered further that the amount of seed crystalline and the moisture content of the syrup solution becomes signifi-cant in terms of crystallization time, when the seed crystals do not have the same contents or represent the same type of crystals as that employed in the syrup solution. It has been found that the amount of seed crystals employed should be greater than 2% by weight, based on the total solids present in the syrup solution, and more particularly should range from 5% to 15% by weight, which is the preferred amount em-plo~ea .
The seed crystals employed in the process may bederived from any source, but typically should represent pure fructose crystals, a mixture of glucose and fructose crystals, or should represent a part of the ~inished crystalline product obtained in the process and recycled in a subsequent crystalli-zation process. In any event, it is important to employ the seed crystals in the same general type, character and nature of that of the composition of the sugar in the aqueous syrup composition, since variations in the nature of the seed crys-tals from that of the syrup composition affect the crystalliza-tion time.
Typically the seed crystals should be added to the syrup composition, when the syrup composition is at a tempera-ture ranging from about 120F to 160~F, and more particularly about 130F to 140F. The syrup composition, after seeding, may be deposited in a mold or other suitable container and then allowed to sit at 50F to 80F and a relative humidity of 35%
to 45% for a crystallization time from about 6 to 72 hours.
Pure fructose syrups may take only a short period of time, for example, as low as 3 to 4 hours, while corn-syrup compositions, that is, containing a mixture of glucose and fructose, typically take a longer period of tlme, such as, for example, 36 to 72 hours. At the end of such crystallization time, the crystalline material is recovered and dried, with the method of drying de-pending upon the moisture content desired in the final product, ~Q~S~4 and then ground to produce the free-flowing, anhydrous, cr~s-talline fructose and glucose of the invention. If desired and preferably, a small percentage of the recovered material then may be recycled and used as a seed crystal with the same type of syrup composition.
In regards to the concentration range of the syrup composition, the syrup concentration is critical, since it has been discovered that, if the range is generally below about 88% by weight, the solution remains pasty, even after the addi-tion of seed crystals, and any crystallization produced is in apaste-type form which is hard and impossible to bring into a dry, free-flowiny, anhydrous, powder form. I-f the syrup com-position exceeds g~nerally about 96% by weight, the s~rup com-position remains as a rather glassy-type syrup mixture. During the crystallization time, the seeded syrup mixture is allowed to sit generally at temperatures of ~rom about 60F to 85 F
such as, for example, 70F to 80F and a relative humidity of 35% to 45%, until substantial crystallization takes place, with the physical condition of the final crystalline product depending in part upon the moisture content of the starting syrup solution.
It has been found that the crystalline product pro-duced by the process is formed in large pellets in the crys-tallization process' for example, about 3 grams in weight, and the crystallization pellets so formed are quite heat-sensi-tive. The crystallization pellets have been found not to lose moisture during drying a~ter a certain moisture content is reached; for example, 3% to 5%. For example, hemispherical pellets, with a base diameter of about 0.75 inches, do not lose moisture beyond about 3%. Attempts to dry such pellets to a lower moisture content, by subjecting the pellets to higher drying temperatures and vacuum, have been unsuccessful, ~ 9 5~ ~ ~
as the surface tends to dry, but the inside material of the pellets only soft~ns.
It has been ~ound that the heat-sensitive, water-soluble crystallization pellets of the process may be dried to a desired moisture content by cooling the pellets to a temperature below about 34F and then granulating the pellets, such as by grinding, to less than 18 mesh. ~h~r~after, the ground pellets may be dried in a low relative humidity, for example, less than 50%, such as 35% to 45%, at oven tempera-tures; for example, 110F to 160~F, to provide free powdered material with a low moisture content, for example, 0.5% to 2%.
Thus the high heat sensitivity of the crystallization pellets makes the product difficult to grind, since the product tends to melt due to heat buildup in the grinding mill. However, the pellets, when cooled to 34F or below, may be ground, and, thereafter, may be dried in conventional ovens to a low mois-ture content.
For the purpose of illustration only, our process will be described in connection with certain preferred operat-ing embodiments; however, it is recognized that various changesand modifications in the process, as described and illustrated, may be made by those persons skilled in the art, all within the spirit and scope of our invention.
Example 1 The term "high-fructose corn syrup" used in this example is used for the following commercially available pro-duct:
Dry Basis Composition Ash (Sulfated) .03%
Carbohydrate components:
Fructose 90%
Dextrose 7%
Other saccharides 3%
Typical analysis:
Solids 80%
Moisture 20%
,, ~ .
~ , .
~S9~4 The syrup was cooked to a moisture content of 92 ~
0.5% and seeded with 5% seed of a size of 177 to 250 microns.
The product was placed in molds and allowed to sit at 78F
and a relative humidity of 30%. The crystalliæation commenced in 24 hours. The resultant product was dried in a vacuum oven maintained at 29" of Hg. The temperature was gradually in-creased from 70F to 200F in 16 hours. The product was worked up to the required par~icle size, Free-flowing, nontacky, crystalline material was obtained.
Some cooked syrup was seeded with the product obtain-ed above the crystallization time reduced to 8 hours.
Example-2 Pure fructose was dissolved in water to obtain a syrup o~ 95% solids content. This was seeded with 5% crystal-line fructose of a size of 74 to 177 microns, deposited in molds and was allowed to sit for 72 hours at 80F and a rela-tive humidity of 45%, and then worked up and dried in the oven by gradually increasing the temperature ~rom 70F to 200F in 4 hours. The product was free-flowing and nontacky.
Exam~le 3 Pure fructose was dissolved in water to obtain a syrup o~ 93% solids content. It was brought to a temperature of 140F and seeded with 10% crystalline fructose of a size of 74 to 174 microns. The resultant material was deposited in molds and allowed to crystallize at 85F and a relative humid ity of 45%. After 12 hours, it was dried and ground. The product was free-flowing, nontacky and crystalline.
Example 4 A 2-pound sample of the crystallization-pellet mat-erial of the process was cooled and ground in a domestic blend-er. The resulting powder was then screened through an 18-mesh screen. The undersized product was dried in a temperature-g _ , '::
`': ' ., ,~ , 5gO~
controlled oven in the presence of circulating air as follows,to provide a low, moisture-free, flowing product:
TIME TEMPERATURE MOISTURE CONTENT
8 110F 2%
4 150F 1%
Attempts to dry the same pellet material, by con-ventional oven-drying of the pellets to low moisture content, were unsuccessful.
As can be seen by the aforesaid data and examples, the syrup concentration and the nature of the seed crystals and crystallization conditions and more specifically relative humidity are essential conditions, in order to produce and provide for the advantages of our process.
r .: ~
Claims (17)
1. A process for the manufacture of an anhydrous, free-flowing crystalline, fructose-containing material, which pro-cess comprises:
a) providing an aqueous fructose-containing composi-tion having a weight of from about 88% to 96% by weight of fructose or a mixture of fructose and glucose, and which solu-tion is essentially free from discoloration;
b) seeding said fructose-containing solution with from about 2% to 15%, based on the total weight of the solu-tion, with seed crystals of -the same general composition as the composition of the solution, and having a particle size of not greater than about 250 microns and at a temperature of from about 120°F to 160°F;
c) permitting such seeded syrup solution to stand at about 50°F to 90°F and at a relative humidity below 70%, to provide for substantial crystallization of the fructose and/or glucose in the solution; and, thereafter, d) recovering the crystallized fructose from the crystallization solution and drying the fructose so recovered, to provide for a free-flowing anhydrous, crystalline fructose or mixture of fructose and glucose.
a) providing an aqueous fructose-containing composi-tion having a weight of from about 88% to 96% by weight of fructose or a mixture of fructose and glucose, and which solu-tion is essentially free from discoloration;
b) seeding said fructose-containing solution with from about 2% to 15%, based on the total weight of the solu-tion, with seed crystals of -the same general composition as the composition of the solution, and having a particle size of not greater than about 250 microns and at a temperature of from about 120°F to 160°F;
c) permitting such seeded syrup solution to stand at about 50°F to 90°F and at a relative humidity below 70%, to provide for substantial crystallization of the fructose and/or glucose in the solution; and, thereafter, d) recovering the crystallized fructose from the crystallization solution and drying the fructose so recovered, to provide for a free-flowing anhydrous, crystalline fructose or mixture of fructose and glucose.
2. The process of claim 1 wherein the seed crystals have a particle size of from about 50 to 200 microns.
3. The process of claim 1 wherein the concentration of the syrup solution ranges from about 90% to 95% by weight.
4. The process of claim 1 wherein the crystallization is carried out at a temperature of from about 50°F to 90°F and the temperature is decreased sequentially from seeding tempera-ture to this range.
5. The process of claim 1 wherein the crystallization time ranges from about 12 to 72 hours.
6. The process of claim 1 wherein the amount of seed crystals employed ranges from about 5% to 15% by weight.
7. The process of claim 1 wherein the solution comprises a high-fructose corn-syrup solution.
8. The process of claim 1 wherein the solution com-prises a sugar-fructose solution of from about 92% to 94% by weight fructose or a mixture of fructose and glucose.
9. The process of claim 1 wherein the relative humidity of the surrounding air during crystallization is maintained from about 35% to 45%.
10. The process of claim 1 wherein the seeded syrup solution is allowed to stand for a period of time ranging from about 6 to 72 hours at a temperature of from about 50°F
to 120°F and the temperature is decreased sequentially and the relative humidity maintained below 50%.
to 120°F and the temperature is decreased sequentially and the relative humidity maintained below 50%.
11. The process of claim 1 which includes grinding the crystallized, recovered fructose at a temperature of below about 34°F, and, thereafter, drying the ground fructose to a moisture content of about 2% or less.
12. The process of claim 1 wherein the seed crystals are derived from a syrup solution of essentially the same com-position and from a prior process.
13. A process for the manufacture of free-flowing, an-hydrous, fructose-containing, crystalline particles, which process comprises:
a) providing for a fructose- or fructose/glucose-containing syrup solution having a weight of from about 90%
to 95% by weight of fructose or fructose and glucose, and which solution is essentially free from discoloration, b) seeding said syrup solution with from about 2%
to 15% by weight of fructose seed crystals, wherein the cry-stals have a particle size ranging from about 50 to 200 mic-rons, the seeding carried out at a temperature of from about 120°F to 160°F, the seed crystals derived from the crystals obtained from the same syrup of a prior process;
c) allowing the seeded syrup solution to stand at a temperature of from about 60°F to 85°F and a relative humid-ity less than 70% for a period of time of from about 6 to 72 hours, to permit the crystallization of the fructose or glucose/fructose from the seeded syrup solution, and d) recovering the crystalline fructose and fructose/
glucose from the solution, and drying the recovered fructose, to produce a free-flowing, anhydrous, crystalline fructose or glucose/fructose mixture.
a) providing for a fructose- or fructose/glucose-containing syrup solution having a weight of from about 90%
to 95% by weight of fructose or fructose and glucose, and which solution is essentially free from discoloration, b) seeding said syrup solution with from about 2%
to 15% by weight of fructose seed crystals, wherein the cry-stals have a particle size ranging from about 50 to 200 mic-rons, the seeding carried out at a temperature of from about 120°F to 160°F, the seed crystals derived from the crystals obtained from the same syrup of a prior process;
c) allowing the seeded syrup solution to stand at a temperature of from about 60°F to 85°F and a relative humid-ity less than 70% for a period of time of from about 6 to 72 hours, to permit the crystallization of the fructose or glucose/fructose from the seeded syrup solution, and d) recovering the crystalline fructose and fructose/
glucose from the solution, and drying the recovered fructose, to produce a free-flowing, anhydrous, crystalline fructose or glucose/fructose mixture.
14. The process of claim 13 which includes grinding the crystallized, recovered fructose or glucose/fructose at a temperature of below about 34°F, and, thereafter, drying the ground fructose or glucose/fructose to a moisture content of about 2% or less.
15. The process of claim 14 which includes drying the fructose or fructose/glucose at a relative humidity of less than 50% and at an oven temperature of from 110° to 160°F to provide a free powdered material having a moisture content of 0.5 to 2% by weight.
16. The process of claim 14 which includes grinding the fructose or fructose/glucose to a mesh size of less than about 18 mesh.
17. The process of claim 13 which includes allowing the seeded syrup solution to stand for a period of 36 to 72 hours.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/029,699 US4199373A (en) | 1979-04-13 | 1979-04-13 | Process for the manufacture of crystalline fructose |
| US29,699 | 1979-04-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1095904A true CA1095904A (en) | 1981-02-17 |
Family
ID=21850400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA348,491A Expired CA1095904A (en) | 1979-04-13 | 1980-03-26 | Process for the manufacture of crystalline fructose |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4199373A (en) |
| EP (1) | EP0017778B1 (en) |
| CA (1) | CA1095904A (en) |
| DE (1) | DE3060092D1 (en) |
| DK (1) | DK155080A (en) |
| PT (1) | PT71086A (en) |
Families Citing this family (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4379171A (en) * | 1981-10-07 | 1983-04-05 | General Mills, Inc. | Method for preparing food products with sweet fructose coatings |
| US4517021A (en) * | 1983-10-28 | 1985-05-14 | A. E. Staley Manufacturing Company | Semi-crystalline fructose |
| US4724006A (en) * | 1984-03-09 | 1988-02-09 | A. E. Staley Manufacturing Company | Production of crystalline fructose |
| US4643773A (en) * | 1984-03-09 | 1987-02-17 | A. E. Staley Manufacturing Company | Crystallization of fructose utilizing a mixture of alcohols |
| JPS61103889A (en) * | 1984-10-24 | 1986-05-22 | Hayashibara Biochem Lab Inc | Crystalline erlose, honey-containing crystal containing said compound, their preparation and use |
| GB8506482D0 (en) * | 1985-03-13 | 1985-04-17 | Tate & Lyle Plc | Sugar process |
| US5350456A (en) * | 1987-02-02 | 1994-09-27 | A. E. Staley Manufacturing Company | Integrated process for producing crystalline fructose and a high fructose, liquid-phase sweetener |
| US5656094A (en) * | 1987-02-02 | 1997-08-12 | A.E. Staley Manufacturing Company | Integrated process for producing crystalline fructose and a high-fructose, liquid phase sweetener |
| US5230742A (en) * | 1987-02-02 | 1993-07-27 | A. E. Staley Manufacturing Co. | Integrated process for producing crystalline fructose and high-fructose, liquid-phase sweetener |
| US5234503A (en) * | 1987-02-02 | 1993-08-10 | A.E. Saley Manufacturing Co. | Integrated process for producing crystalline fructose and a high-fructose, liquid-phase sweetener |
| US5456932A (en) * | 1987-04-20 | 1995-10-10 | Fuisz Technologies Ltd. | Method of converting a feedstock to a shearform product and product thereof |
| US5387431A (en) * | 1991-10-25 | 1995-02-07 | Fuisz Technologies Ltd. | Saccharide-based matrix |
| US4816268A (en) * | 1987-08-14 | 1989-03-28 | Nutrasweet Co | Process for preparing a comestible containing stirrer straw and product thereof |
| US5039346A (en) * | 1988-03-25 | 1991-08-13 | A. E. Staley Manufacturing Company | Fructose syrups and sweetened beverages |
| US4895601A (en) * | 1988-12-12 | 1990-01-23 | Archer Daniels Midland Company | Aqueous-alcohol fructose crystallization |
| US5047088A (en) * | 1989-06-30 | 1991-09-10 | A. E. Staley Manufacturing Company | Method for crystallization of fructose |
| ATE176503T1 (en) * | 1991-08-20 | 1999-02-15 | Staley Mfg Co A E | LIQUID SWEETENER CONTAINING FRUCTOSE AND DEXTROSE |
| US5576042A (en) * | 1991-10-25 | 1996-11-19 | Fuisz Technologies Ltd. | High intensity particulate polysaccharide based liquids |
| DE69231281T2 (en) * | 1991-12-17 | 2001-03-01 | Biovail Tech Ltd | COMPOSITION AND METHOD FOR ULCUS PREVENTION AND TREATMENT |
| CN1042237C (en) * | 1993-04-01 | 1999-02-24 | A.E.施塔利制造公司 | Integrated process for producing crystalline fructose |
| US5597416A (en) * | 1993-10-07 | 1997-01-28 | Fuisz Technologies Ltd. | Method of making crystalline sugar and products resulting therefrom |
| US5445769A (en) * | 1994-06-27 | 1995-08-29 | Fuisz Technologies Ltd. | Spinner head for flash flow processing |
| US5582855A (en) * | 1994-07-01 | 1996-12-10 | Fuisz Technologies Ltd. | Flash flow formed solloid delivery systems |
| US5556652A (en) * | 1994-08-05 | 1996-09-17 | Fuisz Technologies Ltd. | Comestibles containing stabilized highly odorous flavor component delivery systems |
| FI97625C (en) * | 1995-03-01 | 1997-01-27 | Xyrofin Oy | Method for crystallization of xylose from aqueous solutions |
| FI952065A0 (en) * | 1995-03-01 | 1995-04-28 | Xyrofin Oy | Foilfarande Foer tillvaratagande av en kristalliserbar organisk foerening |
| US5587198A (en) * | 1995-05-31 | 1996-12-24 | Fuisz Technologies Ltd. | Positive hydration method of preparing confectionery and product therefrom |
| DE19536792A1 (en) * | 1995-10-02 | 1997-04-03 | Basf Ag | Process for the separation of substances from a liquid mixture by crystallization |
| DE69818023T2 (en) * | 1998-07-08 | 2004-07-08 | S.A. Warcoing | Process for the production of crystal fructose |
| BR0103406A (en) * | 2001-08-15 | 2004-05-04 | Getec Guanabara Quimica Ind S | Process of producing high purity crystalline fructose using low fructose syrup originating from sucrose and product obtained |
| WO2007079606A1 (en) * | 2006-01-06 | 2007-07-19 | Bioright Worldwide Company Ltd. | A method for preparing high concentration fructose-containing high fructose syrup by crystallization |
| WO2007076640A1 (en) * | 2006-01-06 | 2007-07-12 | Bioright Worldwide Company Ltd. | A method for simultaneously preparing 55 % high fructose syrup and 42 % fructose syrup |
| US8249499B2 (en) * | 2009-07-31 | 2012-08-21 | Sierra Wireless, Inc. | Method, system and device for initiating wireless communication |
| US10808002B2 (en) | 2014-10-20 | 2020-10-20 | Cj Cheiljedang Corporation | Method for preparing D-psicose crystal |
| KR101981388B1 (en) * | 2017-06-14 | 2019-05-22 | 씨제이제일제당 (주) | A method of manufacturing a d-psicose crystal |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1640717A (en) * | 1924-09-10 | 1927-08-30 | Int Patents Dev Co | Manufacture of large-grained dextrose |
| FR1534746A (en) * | 1966-04-29 | 1968-08-02 | Boehringer & Soehne Gmbh | Process for obtaining fructose in the crystallized state |
| US3513023A (en) * | 1966-04-29 | 1970-05-19 | Boehringer Mannheim Gmbh | Process for the production of crystalline fructose |
| DE1909316A1 (en) * | 1969-02-25 | 1971-06-24 | Boehringer Mannheim Gmbh | Agglomerated fructose and process for making same |
| LU61049A1 (en) * | 1970-06-03 | 1972-03-22 | ||
| US3718484A (en) * | 1970-08-20 | 1973-02-27 | Food Technology | Solidified product from high fructose corn syrup and process for the preparation thereof |
| FI46631C (en) * | 1971-03-11 | 1973-05-08 | Suomen Sokeri Oy | Process for crystallizing fructose from concentrated aqueous solution |
| US3883365A (en) * | 1972-01-04 | 1975-05-13 | Suomen Sokeri Oy | PH adjustment in fructose crystallization for increased yield |
| DE2229064A1 (en) * | 1972-06-15 | 1973-12-20 | Boehringer Mannheim Gmbh | METHOD FOR PRODUCING FRUCTOSE |
| US3816175A (en) * | 1972-07-03 | 1974-06-11 | Suomen Sokeri Oy | Process for formation of crystalline fructose-glucose blends |
| JPS5239901B2 (en) * | 1973-02-12 | 1977-10-07 | ||
| JPS5012245A (en) * | 1973-06-04 | 1975-02-07 |
-
1979
- 1979-04-13 US US06/029,699 patent/US4199373A/en not_active Expired - Lifetime
-
1980
- 1980-03-18 EP EP80101415A patent/EP0017778B1/en not_active Expired
- 1980-03-18 DE DE8080101415T patent/DE3060092D1/en not_active Expired
- 1980-03-26 CA CA348,491A patent/CA1095904A/en not_active Expired
- 1980-04-10 DK DK155080A patent/DK155080A/en not_active IP Right Cessation
- 1980-04-11 PT PT71086A patent/PT71086A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK155080A (en) | 1980-10-14 |
| EP0017778B1 (en) | 1981-11-25 |
| EP0017778A1 (en) | 1980-10-29 |
| US4199373A (en) | 1980-04-22 |
| DE3060092D1 (en) | 1982-01-28 |
| PT71086A (en) | 1980-05-01 |
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